Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems

Definitions

• the present invention relates to 6-(2,4,6-trifluorophenyl)triazolopyrimidines of the formula I
• the invention relates to a process for the preparation of these compounds, preparations comprising them and their use in the control of harmful phytopathogenic fungi.
• 5-Halo-6-(2,4,6-trifluorophenyl)triazolopyrimidines are generally known from WO 98/46607.
• 5-Cyano- and 5-alkoxytriazolopyrimidines are revealed in WO 02/083677.
• Triazolopyrimidines with optically active amino substituents in the 7-position are generally proposed in WO 02/38565.
• the compounds disclosed in the aforesaid documents are suitable for the control of harmful fungi.
• the compounds according to the invention are distinguished from those disclosed in the aforementioned document by the substitution in the 5-position of the triazolopyrimidine backbone.
• the compounds of the formula I have, in comparison with the known compounds, an increased effectiveness or a broadened spectrum of activity against harmful fungi.
• the compounds according to the invention can be obtained in various ways. They are advantageously obtained starting from the 5-halo-6-(2,4,6-trifluorophenyl)triazolo-pyrimidines of the formula II known from WO 98/46607 by reaction with compounds M-X (formula III).
• Compounds III represent, depending on the meaning of the X group to be introduced, an inorganic cyanide or an alkoxide.
• the reaction is advantageously carried out in the presence of an inert solvent.
• the cation M in the formula III is of little significance; for practical reasons, ammonium, tetraalkylammonium or alkali metal or alkaline earth metal salts are usually preferred.
• the reaction temperature is usually from 0 to 120° C., preferably from 10 to 40° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
• R 2 represents hydrogen
• a cleavable protective group is advantageously introduced before reaction with III [cf. Greene, Protective Groups in Organic Chemistry, J. Wiley & Sons (1981)].
• Suitable solvents comprise ethers, such as dioxane, diethyl ether and, preferably, tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane, aromatic hydrocarbons, such as toluene, or acetonitrile.
• ethers such as dioxane, diethyl ether and, preferably, tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane, aromatic hydrocarbons, such as toluene, or acetonitrile.
• reaction mixtures are worked up conventionally, e.g. by mixing with water, separating the phases and possibly chromatographic purification of the crude products.
• Some of the intermediates and final products are obtained in the form of colorless or slightly brownish viscous oils which, under reduced pressure and at moderately elevated temperature, are freed from or purified of volatile constituents.
• the purification can also take place by recrystallization or trituration.
• halogen fluorine, chlorine, bromine and iodine
• alkyl saturated, straight-chain or branched hydrocarbon radicals with 1 to 4, 6 or 8 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl
• haloalkyl straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above: in particular C 1 -C 2 -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trich
• alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, e.g. C 2 -C 6 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-buteny
• haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
• alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, e.g. C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-p
• cycloalkyl saturated, mono- or bicyclic hydrocarbon groups with 3 to 6 or 8 carbon ring members, e.g. C 3 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
• alkylene saturated, straight-chain or branched hydrocarbon radicals with 1 to 4 or 6 carbon atoms which are bonded to the backbone via a double bond, e.g. ⁇ CH 2 , ⁇ CH—CH 3 , ⁇ CH—CH 2 —CH 3 ;
• oxyalkylenoxy unbranched divalent chains formed from 1 to 3 CH 2 groups in which both valencies are bonded to the backbone via an oxygen atom, e.g. OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O.
• R 1 is C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl or C 1 -C 8 -haloalkyl.
• R 1 is C 3 -C 6 -cycloalkyl which can be substituted by C 1 -C 4 -alkyl.
• R 1 and/or R 2 comprise haloalkyl or haloalkenyl groups with a chiral center
• the (S)-isomers are preferred for these groups.
• the (R)-configurated isomers are preferred.
• a preferred embodiment of the invention relates to compounds of the formula I.1:
• Y is hydrogen or C 1 -C 4 -alkyl, in particular methyl and ethyl, and X is cyano, methoxy or ethoxy.
• An additional preferred embodiment of the invention relates to compounds wherein R 1 and R 2 , together with the nitrogen atom to which they are bonded, form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and can comprise an additional heteroatom from the group consisting of O, N and S as ring member and/or can carry one or more substituents from the group consisting of halogen, C 1 -C 6 -alkyl,
• R 1 and R 2 together with the nitrogen atom to which they are bonded, form a piperidinyl, morpholinyl or thio-morpholinyl ring, in particular a piperidinyl ring, which, if appropriate, is substituted by one to three halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl groups.
• Particular preference is given to the compounds wherein R 1 and R 2 , together with the nitrogen atom to which they are bonded, form a 4-methylpiperidine ring.
• An additional preferred object of the invention are compounds I wherein R 1 and R 2 , together with the nitrogen atom to which they are bonded, form a pyrazole ring which, if appropriate, is substituted by one or two halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl groups, in particular by 3,5-dimethyl or 3,5-di(trifluoromethyl).
• R 1 represents CH(CH 3 )—CH 2 CH 3 , CH(CH 3 )—CH(CH 3 ) 2 , CH(CH 3 )—C(CH 3 ) 3 , CH(CH 3 )—CF 3 , CH 2 C(CH 3 ) ⁇ CH 2 , CH 2 CH ⁇ CH 2 , cyclopentyl or cyclohexyl;
• R 2 represents hydrogen or methyl; or R 1 and R 2 together represent —(CH 2 ) 2 CH(CH 3 )(CH 2 ) 2 —, —(CH 2 ) 2 CH(CF 3 )(CH 2 ) 2 — or —(CH 2 ) 2 O(CH 2 ) 2 —.
• the compounds I are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some are systemically effective and they can be used in plant protection as foliar and soil fungicides.
• the compounds I are also suitable for controlling harmful fungi, such as Paecilomyces variotii, in the protection of materials (e.g. wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
• harmful fungi such as Paecilomyces variotii
• materials e.g. wood, paper, paint dispersions, fibers or fabrics
• the compounds I are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds.
• the application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
• the fungicidal compositions generally comprise between 0.1 and 95%, preferably between 0.5 and 90%, by weight of active compound.
• the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active compound per ha.
• active compound of 1 to 1000 g/100 kg, preferably 5 to 100 g per 100 kilograms, of seed are generally necessary.
• the amount of active compound applied depends on the kind of application area and on the effect desired. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.
• the compounds I can be converted to the usual formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
• the application form depends on the respective use intended; it should always guarantee a fine and uniform distribution of the compound according to the invention.
• the formulations are prepared in a known way, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Suitable solvents/auxiliaries for this are in the main:
• Petroleum fractions having medium to high boiling points such as kerosene or diesel fuel, furthermore coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone or highly polar solvents, e.g. dimethyl sulfoxide, N-methylpyrrolidone or water, are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions.
• coal tar oils and oils of vegetable or animal origin
• aliphatic, cyclic and aromatic hydrocarbons e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated na
• Powders, preparations for broadcasting and dusts can be prepared by mixing or mutually grinding the active substances with a solid carrier.
• Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
• Solid carriers are, e.g., mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and plant products, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
• mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,
• the formulations generally comprise between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active compound.
• the active compounds are employed therein in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
• a compound according to the invention 10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other auxiliaries are added. The active compound dissolves on diluting in water.
• a compound according to the invention 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, e.g. polyvinylpyrrolidone.
• a dispersion is formed on diluting in water.
• a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5%). This mixture is introduced into water using an emulsifying apparatus (UltraTurrax) and is converted to a homogeneous emulsion. An emulsion is formed on diluting in water.
• emulsifying apparatus UltraTurrax
• a compound according to the invention 20 parts by weight of a compound according to the invention are reduced to a fine active compound suspension in an agitator ball mill with addition of dispersants and wetting agents and water or an organic solvent.
• a stable suspension of the active compound is formed on diluting in water.
• a compound according to the invention 50 parts by weight of a compound according to the invention are finely milled with addition of dispersants and wetting agents and, using industrial devices (e.g. extrusion, spray tower, fluid bed), are prepared as water-dispersible or water-soluble granules. A stable dispersion or solution of the active compound is formed on diluting in water.
• 75 parts by weight of a compound according to the invention are milled in a rotor-stator mill with addition of dispersants and wetting agents and also of silica gel.
• a stable dispersion or solution of the active compound is formed on diluting in water.
• a compound according to the invention 0.5 part by weight is finely milled and combined with 95.5% of carriers. Standard processes in this connection are extrusion, spray drying or fluid bed. A granule for direct application is thereby obtained.
• the active compounds can be used as such, in the form of their formulations or of the application forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, preparations for broadcasting or granules, by spraying, atomizing, dusting, broadcasting or watering.
• the application forms depend entirely on the intended uses; they should always guarantee the finest possible dispersion of the active compounds according to the invention.
• Aqueous use forms can be prepared from emulsifiable concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water.
• the substances can be homogenized in water, as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers.
• concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil can also be prepared, which concentrates are suitable for dilution with water.
• concentrations of active compound in the ready-for-use preparations can be varied within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
• the active compounds can also be used with great success in the ultra low volume (ULV) process, it being possible to apply formulations with more than 95% by weight of active compound or even the active compound without additives.
• UUV ultra low volume
• Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if appropriate also not until immediately before use (tank mix). These agents can be added to the preparations according to the invention in a weight ratio of 1:10 to 10:1.
• the preparations according to the invention can, in the application form as fungicides, also be present together with other active compounds, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. On mixing the compounds I or the preparations comprising them in the application form as fungicides with other fungicides, in many cases an expansion of the fungicidal spectrum of activity is obtained.
• the active compounds were prepared separately or together as a stock solution with 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent with an emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and appropriately diluted with water to the desired concentration.
• Uniperol® EL wetting agent with an emulsifying and dispersing action based on ethoxylated alkylphenols
• Use example 1 Activity in protective application against powdery mildew on cucumber leaves caused by Sphaerotheca fuliginea
• Leaves of pot-grown cucumber seedlings of the variety “Chinese Snake” in the cotyledon stage were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous suspension of spores of powdery mildew of cucumber ( Sphaerotheca fuliginea ). The plants were subsequently cultivated for 7 days in a greenhouse at temperatures of between. 20 and 24° C. and a relative atmospheric humidity of 60 to 80%. The extent of mildew development was then determined visually in % of infection of the cotyledon area.
• Use example 2 Activity in 1 day protective application against net blotch of barley caused by Pyrenophora teres
• test plants Leaves of pot-grown barley seedlings were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 24 hours after the spray coating had dried on, the test plants were inoculated with an aqueous suspension of spores of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch. The test plants were subsequently placed in a greenhouse at temperatures of between 20 and 24° C. and a relative atmospheric humidity of 95 to 100%. After 6 days, the extent of development of the disease was determined visually in % of infection of the total leaf area.

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• 2004
  • 2004-11-18 JP JP2006540311A patent/JP2007512276A/ja not_active Withdrawn
  • 2004-11-18 EP EP04797968A patent/EP1689750A1/de not_active Withdrawn
  • 2004-11-18 CN CNA2004800345783A patent/CN1886404A/zh active Pending
  • 2004-11-18 WO PCT/EP2004/013063 patent/WO2005058900A1/de not_active Ceased
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